Name:

CHM 332

FOURTH EXAMINATION
All answers should be written on the exam in the spaces provided. Clearly indicate your
answers in the spaces provided; if I have to guess as to what or where your answer is, it is wrong.
Where applicable, outline the logic or mystical principle you used to arrive at your answer, as
partial credit may be awarded for correct approaches.
You may assume that standard work-up conditions (i.e. those required to obtain a stable,
neutral product, like aqueous acid as example) follow each reaction on the exam. Clearly indicate
stereochemistry where appropriate. Be careful not to show stereochemistry where none exists.
This exam is long (as always) for the time allotted. You are strongly advised to read it
through completely before you begin.
(1)..10 pts...................._____
(2)..24 pts....................._____
(3)..21 pts....................._____
(4)..20 pts....................._____
(5)..16 pts....................._____
(6)..12 pts....................._____
TOTAL (103 pts)..........._____
Percentage_____

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1. [10 pts] Name the following molecules according to IUPAC rules:
a.
meta-chloroisobutyl benzene or 1-chloro-3-isobutylbenzene

Cl

b. Name as an aniline compound:

4-chloro-3-nitroaniline
H2N

NO2
Cl

2. [24 pts] Fill in the necessary reagents for each of the following steps (A-H):
D
NO2

NH2

I
N2 +

1. Mg
2. CO2
CO2H

CN
F

A: _(CH3CH2)2CuLi
C: _HNO3, H2SO4
E: _NaNO2, HCl, H2O, 0C or
HNO2, H2SO4, H2O, 0C
G: _CuCN

B: _CH3CH2Cl, AlCl3
D: _H2, Pd/C or
1. Fe or SnCl2, HCl,2. NaOH, H2O
F: _HBF4, heat
H: _H3O+

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3. [21 pts] Provide the appropriate reagents and conditions, or products for the following
transformations, in a single step.
a.
O2N

Br

NaNH2

O2N

NH2

heat
NO2

NO2

b.
H2, Pd/C

c.
CO2CH3

CO2CH3

H3C
heat

CH3

d.
CO2H

KMnO4, H2O
heat

CO2H

e.
O

Br

Br

Cl
AlCl3

f.
Na, NH3

HO3S

HO3S

OCH3

OCH3

g.

NO2

1. SnCl2 or Fe, HCl

2. NaOH, H2O

NH2

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4. [20 pts] Propose a reasonable synthetic route to each of the following compounds, starting from
benzene. Partial credit will be given for approaches without reagents. Remember: Selectivity is
the name of the game-points will be deducted for reactions that result in ortho/para mixtures.
a.

Br

1. HNO3, H2SO4
2. H2, Pd/C
3. acetyl chloride, pyridine
4. Br2, Fe
5. NaOH, H2O

NH2

Need to place a large Ortho-Para director on the ring to cause the para formation. The amine group
can be protected using the acetyl chloride to become a larger ortho-para director than the amine
group itself.
b.
1. SO3, H2SO4
2. HNO3, H2SO4
3. Cl2, Fe
4. NaOH, H2O
5. H2, Pd/C

Cl

H2N

OH

When building a 1,3,5 system, you cannot place an ortho-para director on the ring until two meta
directors are in place. If you convert one of the groups to the Ortho-Para director you want or put
the chlorine in place too early, the ortho-para director takes control and you wont get 1,3,5selectivity.

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5. [16 pts] The following questions apply to the theoretical and historical aspects of benzene:
a. Explain how the monobromination experiment of benzene assisted in the assignment of the
structure of benzene, to which the molecular formula of C6H6 had been assigned. What key
information did this experiment provide?
C6H6

Br2, Fe

C6H5Br (only one product)

If you only get one product, that means that all of the hydrogen atoms are exactly the same (total
symmetry).

b. Explain how the second bromination experiment of bromobenzene assisted in the assignment of
the structure of benzene. What key information was gained from this experiment?
C6H5Br

Br2, Fe

C6H4Br2 (three products)

Only three products were obtained, not four as predicted by Kekule. Both ortho structures were
actually the same. (Lead to concept of resonance.)

c. Explain why 4n+2 is the perfect number of pi electrons for an aromatic system.
Perfect number of pi electrons to completely fill all of the bonding molecular orbitals. Too many
and you have to place electrons in the antibonding high energy orbitals and too few and you have
unpaired electrons in the bonding molecular orbitals (radicals).

d. Explain why every atom in an aromatic system like benzene must be sp2 hybridized.
In order to have conjugation stability (complete delocalization), every atom in the ring system must
have a perpendicular p orbital for the electron density to move through.

6. [12 pts] Short Answer: Answer 3 of the following 5 questions:

a. Circle the compound below that will have a higher wavelength (max) for ultraviolet absorption.
O

The first one is more conjugated higher wavelength.

b. Propose a logical explanation as to why the first molecule shown below has a larger dipole
moment than the second molecule.
O

O
Ph

Ph

Ph

Ph

The first one can be aromatic but only if it polarizes the carbonyl:
O

Ph

Ph

c. When HCl is added to 1,3-butadiene at room temperature or higher, the major product is 1chloro-2-butene. Explain why this forms in preference to 3-chloro-1-butene.
At high temperatures, more energy is available to allow the allylic carbocation intermediate to form
its resonance structure the higher energy primary allylic carbocation but this has the more stable
alkene in its structure so overall its the more stable final product species.
d. Predict which of the two following acids is more acidic. Provide an explanation for the
differences in acidity utilizing inductive and/or resonance effects in your answer (whatever is most
applicable).
O
O2N

O
OH

H3CO

OH

The first compound is more acidic - the anion will be more stable on a ring that has an electronwithdrawing group than on a ring that has an electron-donating group that would destabilize any
extra electron density.

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e. Explain why an acyl group, like that found in acetophenone (shown below), is a meta director.
Use resonance forms in your discussion.
O

Notice that the most electron-rich positions on the ring occur on the positions that are meta to the
group (the ortho and para positions have a full positive charge). As a result, the meta positions are
the most electron-rich and reactive with electrophiles.